Methods for recovering activity of molecular sieve catalysts

ABSTRACT

The invention is directed to a method of rejuvenating silicoaluminophosphate molecular sieve catalyst that has been deactivated hydrothermally as well as a method of using the rejuvenated catalyst to make an olefin product from an oxygenate feed. In particular, the invention is directed to rejuvenating the catalyst by contacting it with warm water, ammonium salts, dilute acids or low pressure steam until the catalytic activity level of the catalyst has been increased to the desired extent.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of copending application Ser. No.11/171,886 filed Jun. 30, 2005, the contents of which are herebyincorporated by reference in its entirety.

FIELD OF THE INVENTION

The invention is directed to a method of rejuvenatingsilicoaluminophosphate molecular sieve catalyst that has beendeactivated hydrothermally as well as a method of using the rejuvenatedcatalyst to make an olefin product from an oxygenate feed. Inparticular, the invention is directed to rejuvenating the catalyst bycontacting it with warm water, ammonium salts, or low pressure steamuntil the catalytic activity level of the catalyst has been increased tothe desired extent.

BACKGROUND OF THE INVENTION

Silicoaluminophosphates (SAPOs) have been used as adsorbents andcatalysts. As catalysts, SAPOs have been used in processes such as fluidcatalytic cracking, hydrocracking, isomerization, oligomerization, theconversion of alcohols or ethers, and the alkylation of aromatics. Theuse of SAPOs in conversion of oxygenates to light olefin products,particularly ethylene and propylene, is becoming of greater interest forlarge scale, commercial production facilities. Catalysts deactivateduring use due to various reasons. Some catalysts are sensitive toexposure to moisture while other catalysts are impacted by the operatingconditions in a reactor. In the methanol to olefins (MTO) process, forexample, SAPO-34 catalyst deactivation can be divided into two types: 1)short term deactivation due to coking; 2) long term deactivation due tohydrothermal aging. The short term deactivation can be completelyreversed by careful coke burning. Activity lost during hydrothermalaging is much more difficult to recover. The present invention providesa method for rejuvenating SAPO catalysts.

As is known in the development of new large scale, commercial productionfacilities in the commodity chemical business, many problems arise inthe scale up from laboratory and pilot plant operations. Although somework has been published relating to the intermediate activities in thecatalyst production-to-use chain, few of the problems associatedtherewith have been addressed. For example, U.S. Pat. No. 4,681,864 toEdwards et al. discuss the use of SAPO-37 molecular sieve as acommercial cracking catalyst. It is disclosed that activated SAPO-37molecular sieve has poor stability, and that stability can be improvedby using a particular activation process. In this process, organictemplate is removed from the core structure of the sieve just prior tocontacting with feed to be cracked. The process calls for subjecting thesieve to a temperature of 400° to 800° C. within the catalytic crackingunit.

U.S. Pat. No. 5,185,310 to Degnan et al. discloses another method ofactivating silicoaluminophosphate molecular sieve compositions. Themethod calls for contacting a crystalline silicoaluminophosphate withgel alumina and water, and thereafter heating the mixture to at least425° C. The heating process is first carried out in the presence of anoxygen depleted gas, and then in the presence of an oxidizing gas. Theobject of the heating process is to enhance the acid activity of thecatalyst. The acid activity is enhanced as a result of the intimatecontact between the alumina and the sieve.

Briend et al., J. PHYS. CHEM. 1995, 99, 8270-8276, teaches that SAPO-34loses its crystallinity when the template has been removed from thesieve and the de-templated, activated sieve has been exposed to air.Data are presented which suggest that over at least the short term, thiscrystallinity loss is reversible. Even over a period of perhaps twoyears, the data suggests that crystallinity loss is reversible whencertain templates are used.

Several patents assigned to ExxonMobil Chemical Company have addressed adiscovery that activated SAPO molecular sieve will exhibit a loss ofcatalytic activity when exposed to a moisture-containingenvironment—both from the ambient humidity as well as the hightemperature steaming environment exposed to the catalyst in theconversion of oxygenates to olefins. These patents have addressedseveral different methods for recovery of catalyst activity. In U.S.Pat. No. 6,639,117, the freeze drying of the catalyst is employed torecover the catalyst activity. In U.S. Pat. No. 6,498,120 and U.S. Pat.No. 6,825,391, a silicoaluminophosphate molecular sieve is rejuvenatedthrough contact of the catalyst with an anhydrous liquid or vapor, inparticular methanol. Another method is disclosed in U.S. Pat. No.6,756,516 in which the catalyst is treated with certain organic nitrogencompounds to protect the catalyst from degradation through exposure tomoisture.

Although it may be possible to use the above techniques to protect acatalyst from the exposure to moisture within an ambient atmosphere,there still remains the need to rejuvenate catalyst that has beendeactivated from exposure to high temperature steam environments.Surprisingly, in light of the observations by ExxonMobil and the otherprior art regarding the deactivation of SAPO catalysts by exposure tomoisture, it has now been discovered that water or ammonium salts can beused to rejuvenate deactivated catalyst, especially SAPO-34 that hasbeen deactivated by high temperature steam.

SUMMARY OF THE INVENTION

In order to overcome the various problems associated with decrease ofactivity of a molecular sieve due to contact with high temperaturesteam, this invention provides a way to rejuvenate the molecular sieve.In general, this invention provides a process for rejuvenating amolecular sieve which comprises providing a deactivated molecular sieveand contacting the molecular sieve with warm water, water vapor orammonium salts until the catalyst activity has been increased by adesired amount.

Preferably, the molecular sieve is a silicoaluminophosphate molecularsieve and its activity is increased by at least about 25% throughcontact with water and preferably by more. While there may be otherliquids mixed with the water, the liquid is at least 50% water. Therealso may be solids, such as ammonium salts dissolved in the liquid.Among the salts that may be used are ammonium nitrate, ammonium chlorideammonium phosphate, ammonium sulfate, ammonium acetate, ammoniumcarbonate, as well as other ammonium salts.

The silicoaluminophosphate molecular sieve is preferably selected fromthe group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17,SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40,SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, the metal containing formsthereof, and mixtures thereof. Preferably, the silicoaluminophosphate isselected from the group consisting of SAPO-18, SAPO-34, SAPO-35,SAPO-44, SAPO-47, the metal containing forms thereof, and mixturesthereof. More preferably, the silicoaluminophosphate is selected fromthe group consisting of SAPO-18 and SAPO-34, the metal containing formsthereof, and mixtures thereof.

In addition to the rejuvenation of the catalyst, the invention comprisesthe use of the catalyst in making an olefin product from anoxygenate-containing feedstock. The method comprises forming arejuvenated molecular sieve; and then contacting the rejuvenatedmolecular sieve with an oxygenate-containing feedstock to produce anolefin product.

The oxygenate-containing feedstock is selected from the group consistingof methanol; ethanol; n-propanol; isopropanol; C₄ to C₂₀ alcohols;methyl ethyl ether; dimethyl ether; diethyl ether; di-isopropyl ether;formaldehyde; dimethyl carbonate; dimethyl ketone; acetic acid; andmixtures thereof. Preferably, the oxygenate-containing feedstock isselected from the group consisting of methanol, dimethyl ether, andmixtures thereof.

It is also desirable that, in the method of making the olefin product,the rejuvenated molecular sieve is contacted with theoxygenate-containing feedstock at a temperature of 200° to 700° C.Preferably the rejuvenated molecular sieve is contacted with theoxygenate-containing feedstock at a WHSV of at least 5 hr⁻¹ andpreferably at least 20 hr⁻¹. It is also preferred that thesilicoaluminophosphate molecular sieve is provided with a bindermaterial.

The invention also provides contacting the olefin product with apolyolefin-forming catalyst under conditions effective to form apolyolefin. The preferred olefin product contains ethylene and/orpropylene, which can be used to form polyethylene and/or polypropylene.The olefin and polyolefin products so formed are also considered to beencompassed by the invention.

DETAILED DESCRIPTION OF THE INVENTION

SAPO molecular sieve catalysts, in particular, are susceptible tostructural changes as a result of continued exposure to even low levelsof moisture. Such authorities as Paulitz et al., MICROPOROUS MATERIALS,2, 223-228 (1994), however, have shown through X-ray diffraction (XRD),nuclear magnetic resonance (NMR), infrared (IR) and nitrogen (N₂)adsorption analyses that the structural change is largely reversible.

The loss of catalytic activity as a result of contact of molecular sievewith moisture at both storage temperatures and at steaming temperatureswithin a reactor present a problem when large quantities of relativelyexpensive catalyst are needed for commercial operations. In order toovercome the various problems associated with decrease of activity of amolecular sieve due to contact with high temperature steam, thisinvention provides a way to rejuvenate the molecular sieve. In general,this invention provides a process for rejuvenating a molecular sievewhich comprises providing a deactivated molecular sieve and contactingthe molecular sieve with warm water, water vapor, dilute acid, orammonium salts such as ammonium acetate, ammonium chloride or ammoniumcarbonate, ammonium phosphate, ammonium sulfate, as well as otherammonium salts, until the catalyst activity has been increased by adesired amount. Preferred dilute acids include nitric acid andhydrochloric acid that are from 0.01 to 2 N, preferably 0.01 to 1 N andmost preferably from 0.01 to 0.5 N.

Preferably, the molecular sieve is a silicoaluminophosphate molecularsieve and its activity is increased by at least about 25% throughcontact with water and preferably by more. While there may be otherliquids mixed with the water, the liquid is at least 50% water. Therealso may be solids, such as salts dissolved in the liquid.

SAPO molecular sieve, as well as catalyst containing SAPO molecularsieve, which exhibits decreased catalytic activity as a result ofhydrothermal deactivation can be rejuvenated by contacting the sieve orcatalyst with water at relatively moderate temperatures from roomtemperature up to 300° C. More specifically, it has been found thatcontact with water at a temperature from about 15° up to 200° C. canmore than double the activity of the catalyst in conversion ofoxygenates to olefins. Preferably the water temperature is from 25° to100° C. and most preferably is about 65° to 90° C.

In this invention, rejuvenation is considered to be demonstrated whenthe rejuvenation process results in a relative increase in catalystactivity of at least 25%. Preferably, the rejuvenation process willresult in an increase in catalyst activity of at least about 50%, mostpreferably at least about 100%, the increase being calculated as thechange before rejuvenation and after rejuvenation on a percent basis.

In general the liquid water or water vapor is contacted with themolecular sieve to be rejuvenated in a batch or continuous process. Ineither process, the water is contacted with the molecular sieve for atime which can range from several minutes to hours or up to severalweeks. Contact can be stopped at the time a desired degree ofrejuvenation has been obtained. Desirably contacting continues until arelative increase in the catalyst activity of at least 25% has beenobtained. Desirably, the water is flowed over the molecular sieve attemperature in the range of from about 25° to 100° C., preferably fromabout 65° to 90° C.

The pressure at which contact between the water in liquid or vapor formand the molecular sieve can vary. Desirably, pressure is in the range offrom vacuum conditions to about 690 kPa (100 psia), preferably fromabout 0 to 345 kPa (0 to 50 psia).

The preferred catalyst that is used in this invention is one thatincorporates a silicoaluminophosphate (SAPO) molecular sieve. Themolecular sieve comprises a three-dimensional microporous crystalframework structure of [SiO₂], [AlO₂] and [PO₂] tetrahedral units. Thistype of framework is effective in converting various oxygenates intoolefin products.

When a silicoaluminophosphate molecular sieve is used in this invention,it has a relatively low Si/Al₂ ratio. In general, the lower the Si/Al₂ratio, the lower the C₁ to C₄ saturates selectivity, particularlypropane selectivity. An Si/Al₂ ratio of less than 0.65 is desirable,with an Si/Al₂ ratio of not greater than 0.40 being preferred, and anSi/Al₂ ratio of not greater than 0.32 being particularly preferred. AnSi/Al₂ ratio of not greater than 0.20 is most preferred.

Silicoaluminophosphate molecular sieves are generally classified asbeing microporous materials having 8, 10, or 12 membered ringstructures. These ring structures can have an average pore size rangingfrom about 3.5 to 15 angstroms. Preferred are the small pore SAPOmolecular sieves having an average pore size of less than about 5angstroms, preferably an average pore size ranging from about 3.5 to 5angstroms, more preferably from 3.5 to 4.2 angstroms. These pore sizesare typical of molecular sieves having 8 membered rings.

The [PO₂] tetrahedral units within the framework structure of themolecular sieve of this invention can be provided by a variety ofcompositions. Examples of these phosphorus-containing compositionsinclude phosphoric acid, organic phosphates such as triethyl phosphate,and aluminophosphates. The phosphorous-containing compositions are mixedwith reactive silicon and aluminum-containing compositions under theappropriate conditions to form the molecular sieve.

The [AlO₂] tetrahedral units within the framework structure can beprovided by a variety of compositions. Examples of thesealuminum-containing compositions include aluminum alkoxides such asaluminum isopropoxide, aluminum phosphates, aluminum hydroxide, sodiumaluminate, and pseudoboehmite. The aluminum-containing compositions aremixed with reactive silicon and phosphorus-containing compositions underthe appropriate conditions to form the molecular sieve.

The [SiO₂] tetrahedral units within the framework structure can beprovided by a variety of compositions. Examples of thesesilicon-containing compositions include silica sols and siliciumalkoxides such as tetra ethyl orthosilicate. The silicon-containingcompositions are mixed with reactive aluminum and phosphorus-containingcompositions under the appropriate conditions to form the molecularsieve.

Substituted SAPOs can also be used in this invention. These compoundsare generally known as MeAPSOs or metal-containingsilicoaluminophosphates. The metal can be alkali metal ions (Group IA),alkaline earth metal ions (Group IIA), rare earth ions (Group IIIB,including the lanthanoid elements: lanthanum, cerium, praseodymium,neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium,erbium, thulium, ytterbium and lutetium; and scandium or yttrium) andthe additional transition cations of Groups IVB, VB, VIIB, VIIB, VIIIB,and IB.

Preferably, the Me represents atoms such as Zn, Mg, Mn, Co, Ni, Ga, Fe,Ti, Zr, Ge, Sn, and Cr. These atoms can be inserted into the tetrahedralframework through a [MeO₂] tetrahedral unit. The [MeO₂] tetrahedral unitcarries a net electric charge depending on the valence state of themetal substituent. When the metal component has a valence state of +2,+3, +4, +5, or +6, the net electric charge is between −2 and +2.Incorporation of the metal component is typically accomplished addingthe metal component during synthesis of the molecular sieve. However,post-synthesis ion exchange can also be used. In post synthesisexchange, the metal component will introduce cations into ion-exchangepositions at an open surface of the molecular sieve, not into theframework itself.

Suitable silicoaluminophosphate molecular sieves include SAPO-5, SAPO-8,SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35,SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56,the metal containing forms thereof, intergrowths of two or more of theseSAPOs and mixtures thereof. Preferred are SAPO-18, SAPO-34, SAPO-35,SAPO-44, and SAPO-47, particularly SAPO-18 and SAPO-34, including themetal containing forms thereof, intergrowths of two or more of theseSAPOs and mixtures thereof.

An aluminophosphate (ALPO) molecular sieve can also be included in thecatalyst composition. Aluminophosphate molecular sieves are crystallinemicroporous oxides which can have an AlPO₄ framework. They can haveadditional elements within the framework, typically have uniform poredimensions ranging from about 3 angstroms to about 10 angstroms, and arecapable of making size selective separations of molecular species. Morethan two dozen structure types have been reported, including zeolitetopological analogues. Among the aluminophosphates that can be includedare AlPO-5, AlPO-11, AlPO-16, AlPO-17, AlPO-18, AlPO-20, AlPO-31,AlPO-34, AlPO-35, AlPO-36, AlPO-40, AlPO-41, AlPO-42, AlPO-44, andALPO-47. A more detailed description of the background and synthesis ofaluminophosphates is found in U.S. Pat. No. 4,310,440, which isincorporated herein by reference in its entirety. Some preferred ALPOstructures are ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, andALPO-46.

The ALPOs can also include a metal substituent in its framework.Preferably, the metal is selected from the group consisting ofmagnesium, manganese, zinc, cobalt, and mixtures thereof. Thesematerials preferably exhibit adsorption, ion-exchange and/or catalyticproperties similar to aluminosilicate, aluminophosphate and silicaaluminophosphate molecular sieve compositions. Members of this class andtheir preparation are described in U.S. Pat. No. 4,567,029, incorporatedherein by reference in its entirety.

The metal containing ALPOs have a three-dimensional microporous crystalframework structure of MO₂, AlO₂ and PO₂ tetrahedral units. Thesestructures (which contain template prior to calcination) can berepresented by empirical chemical composition, on an anhydrous basis,as:mR:(M_(x)Al_(y)P_(z))O₂wherein “R” represents at least one organic templating agent present inthe intracrystalline pore system; “m” represents the moles of “R”present per mole of (M_(x)Al_(y)P_(z))O₂ and has a value of from zero to0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular metal aluminophosphate involved, “x”, “y”,and “z” represent the mole fractions of the metal “M”, (i.e. magnesium,manganese, zinc and cobalt), aluminum and phosphorus, respectively,present as tetrahedral oxides.

The metal containing ALPOs are sometimes referred to by the acronym asMeAPO. Also in those cases where the metal “Me” in the composition ismagnesium, the acronym MAPO is applied to the composition. SimilarlyZAPO, MnAPO and CoAPO are applied to the compositions which containzinc, manganese and cobalt respectively. To identify the variousstructural species which make up each of the subgeneric classes MAPO,ZAPO, CoAPO and MnAPO, each species is assigned a number and isidentified, for example, as ZAPO-5, MAPO-11, CoAPO-34 and so forth.

The silicoaluminophosphate molecular sieves are synthesized byhydrothermal crystallization methods generally known in the art. See,for example, U.S. Pat. No. 4,440,871; U.S. Pat. No. 4,861,743; U.S. Pat.No. 5,096,684; and U.S. Pat. No. 5,126,308, the methods of making ofwhich are fully incorporated herein by reference. A reaction mixture isformed by mixing together reactive silicon, aluminum and phosphoruscomponents, along with at least one template. Generally the mixture issealed and heated, preferably under autogenous pressure, to atemperature of at least 100° C., preferably from 100° to 250° C., untila crystalline product is formed. Formation of the crystalline productcan take anywhere from around two hours to as much as two weeks.

Typically, the molecular sieve product will be formed in solution. Itcan be recovered by standard means, such as by centrifugation orfiltration. The product can also be washed, recovered by the same meansand dried.

As a result of the crystallization process, the recovered sieve containswithin its pores at least a portion of the template used in making theinitial reaction mixture. The crystalline structure essentially wrapsaround the template, and the template must be removed so that themolecular sieve can exhibit catalytic activity. Once the template isremoved, the crystalline structure that remains has what is typicallycalled an intracrystalline pore system.

In many cases, depending upon the nature of the final product formed,the template may be too large to be eluted from the intracrystallinepore system. In such a case, the template can be removed by a heattreatment process. For example, the template can be calcined, oressentially combusted, in the presence of an oxygen-containing gas, bycontacting the template-containing sieve in the presence of theoxygen-containing gas and heating at temperatures from 200° to 900° C.In some cases, it may be desirable to heat in an environment having alow oxygen concentration. In these cases, however, the result willtypically be a breakdown of the template into a smaller component,rather than by the combustion process. This type of process can be usedfor partial or complete removal of the template from theintracrystalline pore system. In other cases, with smaller templates,complete or partial removal from the sieve can be accomplished byconventional desorption processes such as those used in making standardzeolites.

The reaction mixture can contain one or more templates. Templates arestructure directing agents, and typically contain nitrogen, phosphorus,oxygen, carbon, hydrogen or a combination thereof, and can also containat least one alkyl or aryl group, with 1 to 8 carbons being present inthe alkyl or aryl group.

Representative templates include tetraethyl ammonium compounds,cyclopentylamine, aminomethyl cyclohexane, piperidine, triethylamine,cyclohexylamine, tri-ethyl hydroxyethylamine, morpholine, dipropylamine(DPA), pyridine, isopropylamine and combinations thereof. The preferredtemplate is a tetraethylammonium compound, such as tetraethyl ammoniumhydroxide (TEAOH), tetraethyl ammonium phosphate, tetraethyl ammoniumfluoride, tetraethyl ammonium bromide, tetraethyl ammonium chloride,tetraethyl ammonium acetate.

The silicoaluminophosphate molecular sieve is typically admixed (i.e.,blended) with other materials. When blended, the resulting compositionis typically referred to as a SAPO catalyst, with the catalystcomprising the SAPO molecular sieve.

Materials which can be blended with the molecular sieve can be variousinert or catalytically active materials, or various binder materials.These materials include compositions such as kaolin and other clays,various forms of rare earth metals, metal oxides, other non-zeolitecatalyst components, zeolite catalyst components, alumina or aluminasol, titania, zirconia, magnesia, thoria, beryllia, quartz, silica orsilica or silica sol, and mixtures thereof. These components are alsoeffective in reducing, inter alia, overall catalyst cost, acting as athermal sink to assist in heat shielding the catalyst duringregeneration, densifying the catalyst and increasing catalyst strength.

Additional molecular sieve materials can be included as a part of theSAPO catalyst composition or they can be used as separate molecularsieve catalysts in admixture with the SAPO catalyst if desired.Structural types of small pore molecular sieves that are suitable foruse in this invention include AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK,CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU,PHI, RHO, ROG, THO, and substituted forms thereof. Structural types ofmedium pore molecular sieves that are suitable for use in this inventioninclude MFI, MEL, MTW, EUO, MTT, HEU, FER, AFO, AEL, TON, andsubstituted forms thereof. These small and medium pore molecular sievesare described in greater detail in the ATLAS OF ZEOLITE STRUCTURALTYPES, W. M. Meier and D. H. Olsen, Butterworth Heineman, 3rd ed., 1997,the detailed description of which is explicitly incorporated herein byreference. Preferred molecular sieves which can be combined with asilicoaluminophosphate catalyst include ZSM-5, ZSM-34, erionite, andchabazite.

The catalyst composition preferably comprises about 1% to about 99%,more preferably about 5% to about 90%, and most preferably about 10% toabout 80%, by weight of molecular sieve. It is also preferred that thecatalyst composition have a particle size of from about 20μ to 3,000μ,more preferably about 30μ to 200μ, most preferably about 50μ to 150μ.

The catalyst can be subjected to a variety of treatments to achieve thedesired physical and chemical characteristics. Such treatments include,but are not necessarily limited to hydrothermal treatment, calcination,acid treatment, base treatment, milling, ball milling, grinding, spraydrying, and combinations thereof.

It is particularly desirable that the rejuvenated molecular sieve ofthis invention be used in the process of making olefin product from anoxygenate-containing feedstock. In one embodiment of this invention, afeed containing an oxygenate, and optionally a diluent or a hydrocarbonadded separately or mixed with the oxygenate, is contacted with acatalyst containing a rejuvenated SAPO molecular sieve in a reactionzone or location. The location in which such contact takes place isherein termed the “reactor,” which may be a part of a “reactorapparatus” or “reaction system.” Another part of the reaction system maybe a “regenerator,” wherein carbonaceous deposits (or coke) on thecatalyst resulting from the olefin conversion reaction are removed bycontacting the catalyst with regeneration medium.

The oxygenate feedstock of this invention comprises at least one organiccompound which contains at least one oxygen atom, such as aliphaticalcohols, ethers, carbonyl compounds (aldehydes, ketones, carboxylicacids, carbonates, esters and the like). When the oxygenate is analcohol, the alcohol can include an aliphatic moiety having from 1 to 10carbon atoms, more preferably from 1 to 4 carbon atoms. Representativealcohols include but are not necessarily limited to lower straight andbranched chain aliphatic alcohols and their unsaturated counterparts.Examples of suitable oxygenate compounds include, but are not limitedto: methanol; ethanol; n-propanol; isopropanol; C₄ to C₂₀ alcohols;methyl ethyl ether; dimethyl ether; diethyl ether; di-isopropyl ether;formaldehyde; dimethyl carbonate; dimethyl ketone; acetic acid; andmixtures thereof. Preferred oxygenate compounds are methanol, dimethylether, or a mixture thereof.

The method of making the preferred olefin product in this invention caninclude the additional step of making the oxygenate feedstock fromhydrocarbons such as oil, coal, tar sand, shale, biomass and naturalgas. Methods for making an oxygenate feedstock are known in the art.These methods include fermentation to alcohol or ether, making synthesisgas, and then converting the synthesis gas to alcohol or ether.Synthesis gas can be produced by known processes such as steamreforming, autothermal reforming and partial oxidization.

One or more inert diluents may be present in the feedstock, for example,in an amount of from 1 to 99 mol-%, based on the total number of molesof all feed and diluent components fed to the reaction zone (orcatalyst). As defined herein, diluents are compositions which areessentially non-reactive across a molecular sieve catalyst, andprimarily function to make the oxygenates in the feedstock lessconcentrated. Typical diluents include, but are not necessarily limitedto helium, argon, nitrogen, carbon monoxide, carbon dioxide, water,essentially non-reactive paraffins (especially the alkanes such asmethane, ethane, and propane), essentially non-reactive alkylenes,essentially non-reactive aromatic compounds, and mixtures thereof. Thepreferred diluents are water and nitrogen. Water can be introduced ineither liquid or vapor form.

Hydrocarbons can also be included as part of the feedstock, i.e., asco-feed. As defined herein, hydrocarbons included with the feedstock arehydrocarbon compositions which are converted to another chemicalarrangement when contacted with molecular sieve catalyst. Thesehydrocarbons can include olefins, reactive paraffins, reactivealkylaromatics, reactive aromatics or mixtures thereof. Preferredhydrocarbon co-feeds include, propylene, butylene, pentylene, C₄ ⁺hydrocarbon mixtures, C₅ ⁺ hydrocarbon mixtures, and mixtures thereof.More preferred as co-feeds are C₄ ⁺ hydrocarbon mixtures, with the mostpreferred being C₄ ⁺ hydrocarbon mixtures which are obtained fromseparation and recycle of reactor product.

In the process of this invention, coked catalyst can be regenerated bycontacting the coked catalyst with a regeneration medium to remove allor part of the coke deposits. This regeneration can occur periodicallywithin the reactor by ceasing the flow of feed to the reactor,introducing a regeneration medium, ceasing flow of the regenerationmedium, and then reintroducing the feed to the fully or partiallyregenerated catalyst. Regeneration may also occur periodically orcontinuously outside the reactor by removing a portion of thedeactivated catalyst to a separate regenerator, regenerating the cokedcatalyst in the regenerator, and subsequently reintroducing theregenerated catalyst to the reactor. Regeneration can occur at times andconditions appropriate to maintain a desired level of coke on the entirecatalyst within the reactor.

At any given instant in time, some of the catalyst in the reactor willbe fresh, some regenerated, and some coked or partially coked as aresult of having not yet been regenerated. Therefore, various portionsof the catalyst in the reactor will have been feedstock exposed fordifferent periods of time. Since the rate at which feed flows to thereactor can vary, the amount of feed to which various portions of thecatalyst can also vary.

Any standard reactor system can be used, including fixed bed, fluid bedor moving bed systems. Reactors that can be used include riser reactorsand short contact time countercurrent free-fall reactors in which anoxygenate feedstock can be contacted with a molecular sieve catalyst ata WHSV of at least about 5 hr⁻¹, preferably in the range of from about20 to 1000 hr⁻¹, and most preferably in the range of from about 20 to500 hr⁻¹. WHSV is defined herein as the weight of oxygenate, andhydrocarbon which may optionally be in the feed, per hour per weight ofthe molecular sieve content of the catalyst. Because the catalyst or thefeedstock may contain other materials which act as inerts or diluents,the WHSV is calculated on the weight basis of the oxygenate feed, andany hydrocarbon which may be present, and the molecular sieve containedin the catalyst.

Preferably, the oxygenate feed is contacted with the rejuvenatedcatalyst when the oxygenate is in a vapor phase. Alternately, theprocess may be carried out in a liquid or a mixed vapor/liquid phase.When the process is carried out in a liquid phase or a mixedvapor/liquid phase, different conversions and selectivities offeed-to-product may result depending upon the catalyst and reactionconditions.

The process can generally be carried out at a wide range oftemperatures. An effective operating temperature range can be from about200° to 700° C., preferably from about 300° to 600° C., more preferablyfrom about 350° to 550° C. At the lower end of the temperature range,the formation of the desired olefin products may become markedly slow.At the upper end of the temperature range, the process may not form anoptimum amount of product. The pressure also may vary over a wide range,including autogenous pressures.

In a preferred embodiment of the continuous operation, only a portion ofthe catalyst is removed from the reactor and sent to the regenerator toremove the accumulated coke deposits that result during the catalyticreaction. In the regenerator, the catalyst is contacted with aregeneration medium containing oxygen or other oxidants. Examples ofother oxidants include O₃, SO₃, N₂O, NO, NO₂, N₂O₅, and mixturesthereof. It is preferred to supply O₂ in the form of air. The air can bediluted with nitrogen, CO₂, or flue gas, and steam may be added.Desirably, the O₂ concentration in the regenerator is reduced to acontrolled level to minimize overheating or the creation of hot spots inthe spent or deactivated catalyst. The deactivated catalyst also may beregenerated reductively with H₂, CO, mixtures thereof, or other suitablereducing agents. A combination of oxidative regeneration and reductiveregeneration can also be employed.

In essence, the coke deposits are removed from the catalyst during theregeneration process, forming a regenerated catalyst. The regeneratedcatalyst is then returned to the reactor for further contact with thefeed. Typical regeneration temperatures are in the range of 250° to 700°C., desirably in the range of 350° to 700° C. Preferably, regenerationis carried out at a temperature range of 450° to 700° C.

It is desirable to strip at least some of the volatile organiccomponents which may be adsorbed onto the catalyst or located within itsmicroporous structure prior to entering the regenerator. This can beaccomplished by passing a stripping gas over the catalyst in a stripperor stripping chamber, which can be located within the reactor or in aseparate vessel. The stripping gas can be any substantially inert mediumthat is commonly used. Examples of stripping gas are steam, nitrogen,helium, argon, methane, CO₂, CO, flue gas, and hydrogen.

It may be desirable to cool at least a portion of the regeneratedcatalyst to a lower temperature before it is sent back to the reactor. Aheat exchanger located externally to the regenerator may be used toremove some heat from the catalyst after it has been withdrawn from theregenerator. When the regenerated catalyst is cooled, it is desirable tocool it to a temperature which is from about 200° C. higher to about200° C. lower than the temperature of the catalyst withdrawn from thereactor. More desirably, it is cooled to a temperature from about 10° to200° C. lower than the temperature of the catalyst withdrawn from thereactor. This cooled catalyst then may be returned to either someportion of the reactor, the regenerator, or both. When the regeneratedcatalyst from the regenerator is returned to the reactor, it may bereturned to the reactor's catalyst disengaging zone, the reaction zone,and/or the inlet zone. Introducing the cooled catalyst into the reactoror regenerator serves to reduce the average temperature in the reactoror regenerator. The catalyst may also be cooled with water in accordancewith the present invention.

The reactor and regenerator may be configured such that the feedcontacts the regenerated catalyst before it is returned to the reactor.In an alternative embodiment, the reactor and regenerator are configuredsuch that the feed contacts the regenerated catalyst after it isreturned to the reactor. In yet another embodiment, the feed stream canbe split such that feed contacts regenerated catalyst before it isreturned to the reactor and after it has been returned to the reactor.

It is preferred the catalyst within the reactor have an average level ofcoke effective for selectivity to ethylene and/or propylene. The averagecoke level on the catalyst will be from about 2 to about 10 wt-%. Inorder to maintain this average level of coke on catalyst, the entirevolume of catalyst can be partially regenerated under conditionseffective to maintain the desired coke content on catalyst. It ispreferred, however, to recycle only a portion of the coked catalyst forfeed contact without regenerating. This recycle can be performed eitherinternal or external to the reactor. The portion of coked catalyst to beregenerated is preferably regenerated under conditions effective toobtain a regenerated catalyst having a coke content of less than 2 wt-%.

In order to make up for any catalyst loss during the regeneration orreaction process, fresh catalyst can be added. The fresh catalyst mayeither be added to the regenerated catalyst after it is removed from theregenerator, and then both are added to the reactor or the freshcatalyst may be added to the reactor independently of the regeneratedcatalyst.

One skilled in the art will also appreciate that the olefins produced bythe oxygenate-to-olefin conversion reaction of the present invention canbe polymerized to form polyolefins, particularly polyethylene andpolypropylene. Processes for forming polyolefins from olefins are knownin the art. In addition to polyolefins, numerous other olefinderivatives may be formed from the olefins recovered therefrom. Theseinclude, but are not limited to, aldehydes, alcohols, acetic acid,linear alpha olefins, vinyl acetate, ethylene dichloride and vinylchloride, ethylbenzene, ethylene oxide, cumene, isopropyl alcohol,acrolein, allyl chloride, propylene oxide, acrylic acid,ethylene-propylene rubbers, and acrylonitrile, and trimers and dimers ofethylene, propylene or butylenes. The methods of manufacturing thesederivatives are well known in the art, and therefore, are not discussedherein.

This invention will be better understood with reference to the followingexample, which is intended to illustrate specific embodiments within theoverall scope of the invention as claimed.

EXAMPLE

A SAPO-34 catalyst was obtained that was made according to the followingprocess: In a container orthophosphoric acid (85%) was combined withwater. To this there was added a silica sol and a 35 wt. % aqueoussolution of tetraethylammonium hydroxide (TEAOH). Finally, alumina inthe form of pseudo-boehmite along with water and SAPO-34 seed materialwere added and blended in. The mixture was now placed in a steelpressure reactor equipped with a turbine stirrer. The mixture was nowstirred and heated to 100° C. over a 6 hour period, held at 100° C. for6 hours, then heated to 175° C. over a period of 3 hours and held therefor the reaction time of 24 hours. Finally, the reaction mixture wascooled to ambient temperature and the solid product recovered bycentrifugation and washed with water. Then, a coked MTO catalyst,removed from a demonstration plant, that comprised 40 wt-% SAPO-34+binder was first calcined to remove coke (Sample I). The sample was thenhydrothermally treated at 700° C., 1 atm H₂O for 800 hours (Sample II).A series of treatments as outlined below were done to the hydrothermallydeactivated sample. All treated samples were then dried at 120° C.overnight and followed by exposure to ambient conditions for 48 hours toachieve a consistent LOI on the samples. The samples were then sent fora microreactor test to determine activity of the sample.

Sample and treatment description and catalyst activity K-Oxygenate(volumetric rate Sample # Description constant 1/s) 1 Starting materialthat has been regenerated (550° C., 15 370 hours). Dried at 120° C.,then left at room temperature for 48 hours. 2 Regenerated catalyst issteamed at 700° C. for 800 hours at 1 atm 106 water pressure. Dried at120° C., then at room temperature for 48 hours. 3 Rejuvenated withdistilled water at room temperature for 4 144 hours, washed 5 times with50 ml distilled water, dried at 120° C., then left open to air for 48hours. 4 Rejuvenated with distilled water at 85° C. for 4 hours, washed204 5 times with 50 ml distilled water, dried at 120° C., then left opento air for 48 hours. 5 Rejuvenated with hot 2N NH₄NO₃, dissolved indistilled 195 water at 85 C. for 4 hours, washed 5 times with 50 mldistilled water, dried at 120° C., then left open to air for 48 hours,calcined at 650° C. for 5 hours, left open to air for 48 hours. 6Rejuvenated with steaming at 150° C. for 4 hours in N₂, 25% 125 steam(200 torr H₂O) dried at 120° C., then left open to air for 48 hours. 7Rejuvenated with steaming at 200° C. for 4 hours in N₂, 25% 126 steam(200 torr H₂O) dried at 120° C., then left open to air for 48 hours.

In the microreactor reactivity test, 150 mg of catalyst is loaded into a8 mm ID quartz reactor with sintered glass frit at the middle of thereactor to keep catalyst in place. Catalyst is first pretreated at 500°C. for 1 hour in dry N₂. Reactor temperature is then lowered to 450° C.and methanol feed is introduced. Methanol feed is introduced by passinga stream of N₂ (350 cc/min) through a 3-leg saturator filled withmethanol and set in at 5° C. constant temperature bath. An online GC isattached to the plant for product analysis. According to literature,reaction rate is assumed to be first order with regard to oxygenatesconcentration. Catalyst activity is expressed as first order kineticconstant for oxygenates conversion which is expressed by the equation−kt=ln(1−x) where x is oxygenate conversion, t is space time and k is afirst order kinetic constant. First order kinetic constant for all thecatalysts tested are summarized in the above table. Oxygenatesconversion was determined on a water and coke free basis. It is clearthat treatment of the hydrothermally deactivated catalysts with water orwith water containing ammonium salts resulted in recovery of significantamount of lost activity. It is anticipated that such way for catalystactivity recovery can be applied to other SAPO based molecular sieves.

This invention can be applied in commercial operation wherehydrothermally deactivated catalyst coming out of regenerator can betreated with warm water and the treated catalyst can be returned back toregenerator or reactor directly.

1. A method of making an olefin product from an oxygenate-containingfeedstock, comprising: providing a silicoaluminophosphate molecularsieve having decreased catalytic activity as a result of contact withhigh temperature moisture at between 300° and 600° C. or regenerationtemperatures between 350° and 700° C.; contacting the molecular sievewith low temperature liquid comprising at least 50% water or water vaporwherein said low temperature is between about 15° and 200° C. until thecatalytic activity of said molecular sieve increases at least 25% ascompared to the molecular sieve having decreased catalytic activity; andthen contacting the rejuvenated molecular sieve with anoxygenate-containing feedstock to produce an olefin product.
 2. Themethod of claim 1 wherein said low temperature liquid further comprisesat least one dissolved solid.
 3. The method of claim 1 wherein saiddissolved solid is selected from the group consisting of ammoniumchloride, ammonium phosphate, ammonium sulfate, ammonium acetate,ammonium carbonate, ammonium nitrate and mixtures thereof.
 4. The methodof claim 1 wherein said low temperature liquid is a dilute acid.
 5. Themethod of claim 4 wherein said dilute acid is nitric acid orhydrochloric acid.
 6. The method of claim 1 wherein after said molecularsieve is contacted with low temperature water, said molecular sieve issent to a regeneration zone for removal of coke formed on said molecularsieve.
 7. The method of claim 1 wherein the catalytic activity isincreased by at least 50%.
 8. The method of claim 1 wherein thecatalytic activity is increased by at least 100%.
 9. The method of claim1 wherein the low temperature is between 25° and 100° C.
 10. The methodof claim 1 wherein the low temperature is between 65° and 90° C.
 11. Themethod of claim 1 wherein the silicoaluminophosphate molecular sieve isselected from the group consisting of SAPO-5, SAPO-8, SAPO-1, SAPO-16,SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37,SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, the metalcontaining forms thereof, intergrowths of two or more of saidsilicoaluminophosphate molecular sieves and mixtures thereof.
 12. Themethod of claim 1 wherein the silicoaluminophosphate molecular sieve isselected from the group consisting of SAPO-18 and SAPO-34, the metalcontaining forms thereof, intergrowths and mixtures thereof.
 13. Themethod of claim 1 wherein the oxygenate-containing feedstock is selectedfrom the group consisting of methanol; ethanol; n-propanol; isopropanol;C₄ to C₂₀ alcohols; methyl ethyl ether; dimethyl ether; diethyl ether;di-isopropyl ether; formaldehyde; dimethyl carbonate; dimethyl ketone;acetic acid; and mixtures thereof.
 14. The method of claim 1 wherein therejuvenated molecular sieve is contacted with the oxygenate-containingfeedstock at a temperature of 200° to 700° C.
 15. The method of claim 1wherein the silicoaluminophosphate molecular sieve is provided with abinder material.
 16. The method of claim 1 wherein the olefin product iscontacted with a polyolefin-forming catalyst under conditions effectiveto form a polyolefin.